method of preparing a composite wooden board with a polymeric, thermoset, cured binder

专利摘要:
METHOD OF PREPARING A COLLECTION OF MATERIAL AGGLUTINATED WITH A POLYMERIC, THERMORRIGIDED, CURED AND COMPOSITION BINDING. A binder is disclosed comprising a polymeric binder comprising the products of a carbohydrate reagent and a nucleophile. The binder is useful for the consolidation of a loosely agglomerated material such as fibers. Fibrous products comprising fibers in contact with a carbohydrate reagent and a nucleophile are also disclosed. The binder composition can be cured to produce a fibrous product comprising fibers bonded by a crosslinked polymer. In addition, methods are disclosed for agglutination of fibers with the carbohydrate reagent and polyamine-based binder.
公开号:BR112012028526B1
申请号:R112012028526-2
申请日:2011-05-07
公开日:2020-11-17
发明作者:Charles Appley；Carl Hampson；Gert Mueller；Bénédicte Pacorel
申请人:Knauf Insulation；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED REQUESTS
This application claims the benefit of provisional application US 61 / 332,452, filed on May 7, 2010, which is incorporated by reference into this document. TECHNICAL FIELD
The present invention relates to a binder formulation and materials produced therefrom comprising a carbohydrate-based binder and a method for its preparation. More specifically, a binder is described which comprises the reaction products of a carbohydrate and a nucleophile and materials produced therefrom. FUNDAMENTALS
Binders are useful in the manufacture of articles, as they are able to consolidate non-agglomerated or loosely agglomerated material. Binders allow, for example, two or more surfaces to be joined. More specifically, binders can be used to produce products that comprise consolidated fibers. Thermorigid binders can be characterized by being transformed into insoluble and infusible materials by means of either heat or catalytic action. Examples of a thermoset binder include a variety of phenol-aldehyde, urea-aldehyde, melamine-aldehyde materials and other materials produced by condensation polymerization such as furan and polyurethane resins. Binder compositions containing phenol-aldehyde, resorcinol-aldehyde, phenol / aldehyde / urea, phenol / melamine / aldehyde and the like are used for bonding fibers, textiles, plastics, rubbers and many other materials.
The mineral wool and fiber board industries 5 have historically used a phenol / formic aldehyde binder to bind fibers. Binders of the phenol / formic aldehyde type provide properties suitable for the final products; however, environmental considerations have motivated the development of alternative binders. Such an alternative binder is a carbohydrate-based binder derived from the reaction of a carbohydrate with a multiprotic acid, such as in U.S. published application No. 2007/0027283 and published PCT application W02009 / 019235. Another alternative binder consists of the esterification products of the reaction of a polycarboxylic acid with a polyol, as in U.S. published application No. 2005/0202224.
As these binders do not use formic aldehyde as a reagent, collectives have been referred to as formless aldehyde-free binders. 20 One area of current development is to find a replacement for uncle hay / formic aldehyde binders across the entire product range in the construction and automotive sectors (fiberglass insulation, particle boards, panels for offices, and 25 insulation acoustic). More specifically, the previously developed formic aldehyde-free binders may not have all the desired properties for all products in this sector. Binders based on acrylic acid and poly (vinyl alcohol), for example, 30 showed promising performance characteristics. However, they are relatively more expensive than phenol / formic aldehyde binders, are essentially derived from petroleum-based resources and have a tendency to exhibit lower reaction rates when compared to phenol / formic aldehyde binder compositions (requiring or extended cure times or higher cure temperatures). Carbide-based binder compositions are produced from relatively inexpensive precursors and are mainly derived from renewable resources; however, these binders may also require reaction conditions for curing that are substantially different from the conditions under which the traditional formic phenol / aldehyde binder system is cured. For this reason, it was not easy to obtain a substitution of phenol / formic aldehyde type binders with an alternative binder. SUMMARY
According to the present invention, a carbohydrate-based binder is described. The binder composition has properties that make it useful for a variety of applications; more especially, the binder can be used to loosely bond agglomerated material such as fibers.
In illustrative embodiments, the present invention relates to a binder that comprises a polymeric product of a carbohydrate reagent and a nucleophile. In one embodiment, the carbohydrate reagent is a polysaccharide. In one embodiment, the carbohydrate reagent is a monosaccharide or a disaccharide. In another embodiment, carbohydrate is a monosaccharide in its form of aldose or ketosis. In another embodiment, the carbohydrate reagent is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polymeric product is a heat-corrected polymeric product.
In illustrative modalities, the nucleophile is a difunctional. In another embodiment, the nucleophile is Ri-Q-R2, where Q is alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which is optionally substituted having a nucleophilic moiety and a stabilizing moiety, Ri is selected from the group that consists of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl a carboxyl, a carboxylate, a hydroxyl and an alkoxide and R2 is selected from the group consisting of amine, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol). In one embodiment, the nucleophile includes an amine functional group.
In illustrative modalities, the molar ratio of the carbohydrate reagent to the nucleophile is in the range of approximately 1: 1 to approximately 30: 1. In another embodiment, the molar ratio of the carbohydrate reagent to the nucleophile is in the range of approximately 2: 1 to approximately 10: 1. In another embodiment, an aqueous extract of the polymeric product has a pH in the range of approximately 5 to approximately 9. In another embodiment, an aqueous extract of the polymeric product is essentially colorless. In yet another embodiment, the polymeric product is free of phenol and / or free of formic aldehyde. In another embodiment, an aqueous extract of the polymeric product is capable of reducing Benedict's reagent. In another mode, the polymeric product absorbs light between 400 and 500 nm, for example, in a mode at 420 nm.
In an illustrative embodiment, a method of making a collection of material bound with a polymeric binder comprises preparing a solution that contains reagents for the production of the polymeric binder and a solvent, the reagents including a carbohydrate reagent and a nucleophile; arrange the solution on the material collection; volatilize the solvent to form an uncured product, and subject the uncured product to conditions that cause the carbohydrate reagent and the nucleotide to polymerize to form the polymeric binder. In one embodiment, the material collection comprises fibers selected from the group consisting of mineral fibers (slag wool fibers, rock wool fibers, or glass fibers), aramid fibers, ceramic fibers, metallic fibers, carbon fibers , polyimide fibers, polyester fibers, rayon fibers, and cellulosic fibers. In another embodiment, the material collection comprises particulate material such as coal or sand. In another embodiment, the material collection consists of glass fibers. In another embodiment, glass fibers are present in the range of approximately 70% to approximately 99% by weight. In another modality, the material collection comprises cellulosic fibers. Cellulosic fibers, for example, can consist of wood chips, sawdust, wood pulp or crushed wood. In yet another embodiment, cellulosic fibers can be other natural fibers such as jute, hemp or straw.
In illustrative embodiments, the method of preparing a collection of material bound with a polymeric binder also includes preparing a solution by adding an amount of carbohydrate reagent and an amount of nucleophile so that the molar ratio is in the range from approximately 2: 1 to approximately 10: 1, respectively. In one embodiment, the preparation of the solution includes the addition of the carbohydrate reagent and the nucleophile to an aqueous solution. In another embodiment, the preparation of the solution includes adjusting the pH of the solution to fall in the range of approximately 8 to approximately 13, for example, in a modality in the range of approximately 8 to approximately 12.
In illustrative embodiments, the present invention relates to a composition comprising a collection of material and a binder; the binder comprises the polymeric products of a reaction between a carbohydrate reagent and a nucleophile, the polymeric products being substantially insoluble in water. In one embodiment, the material collection includes mineral fibers (slag wool fibers, rock wool fibers, or glass fibers), aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyimide fibers, polyester, rayon fibers, and cellulosic fibers. Cellulosic fibers include, for example, wood chips, sawdust, wood pulp and / or crushed wood. In one embodiment, the carbohydrate reagent is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the nucleophile is selected from the group consisting of a diamine, triamine, 5 tetramine and pentamine. In one embodiment, the nucleophile is R1-Q-R2, where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted, Ri is a nucleophilic moiety, and R2 is a stabilizing moiety . In one embodiment, Ri is selected from the group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl and a alkoxide. In another embodiment, R2 is selected from the group consisting of an amine, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol).
In another embodiment, the composition further comprises a compound containing silicon. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized alkyl silyl ether, such as, for example, amino silylated alkyl ether. In one embodiment, for example, the silicon-containing compound 25 can be gamma-aminopropyltriethoxy silane, gamma-glydidoxy-propyltrimethoxy silane or aminoethylaminopropyltrimethoxy silane or a mixture thereof. In another embodiment, the silicon-containing compound can be an amino functional oligomeric siloxane. In another embodiment, composition 30 comprises a corrosion inhibitor selected from the group consisting of anti-dust oil, monoammonium phosphate, pentahydrated sodium metasilicate, melamine, tin (II) oxalate and a liquid hydrogenated methyl silicone emulsion. . 5 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a schematic view of a Maillard reaction, which culminates in the production of melanoidins. Figure 2 shows a schematic view of a representative Amadori rearrangement. 10 Figure 3 shows the thermal profile of the cure (Y axis in ° C) of the center of a glass fiber mat sample for different binders during a hot molding cycle (X axis in minutes of molding time) using a molding press with a temperature controlled plate 15 at 204 ° C. Binder 1 (♦) is a phenol / formic aldehyde binder (Comparative example 2); Binder 2 (■) is a carbohydrate / inorganic acid binder (Comparative Example 3); and Binder 3 (X) is a dextrose-ammonia-hexamethylene diamine 20 (HMDA) binder (Example 5). DETAILED DESCRIPTION
Although the invention is subject to several modifications and alternative forms, some specific modalities will be described in this document in 25 details. It should be understood, however, that there is no intention to limit the invention to the specific forms described, but on the contrary, the intention is to cover all modifications, equivalents and alternatives that affect the spirit and scope of the invention.
The present invention relates to a binder composition that has an unexpected utility in consolidating non-agglomerated or loosely agglomerated material. The binder composition represents an unexpected advance in the current state of technology in the field of binder compositions. More specifically, the binder shows improvements in performance and provides more simplified and advantageous manufacturing methodologies, while maintaining solid environmental benefits that are characteristic of a carbohydrate-based binder system.
As used herein, the term binder solution is the solution of chemical substances that can be substantially dehydrated to form an uncured binder. As used in this document, the binder or binder composition can be cured, uncured or partially cured. It refers to the composition of the uncured binder as being an uncured binder composition. An uncured binder is a substantially dehydrated mixture of chemicals that can be cured to form a cured binder. Substantially dehydrated (a) means that the solvent (typically water or an aqueous mixture) used to prepare the binder solution is vaporized to such an extent that the viscosity of the remaining material (including the binder reagents and the solvent) is sufficiently high to create a cohesion between the material loosely agglomerated; thus, the remaining material is an uncured binder. In one embodiment, the solvent constitutes less than 65% of the total weight of the remaining material. In another embodiment, a substantially dehydrated binder has a moisture content between approximately 5% and approximately 65% water by weight of the total binder. In another embodiment, the solvent may make up less than 50% of the total weight of the remaining material. In yet another embodiment, the solvent can make up less than 35% of the total weight of the remaining material. In another embodiment, a substantially dehydrated binder has between approximately 10% and approximately 35% of water by weight of the total binder. In another embodiment, the solvent may make up less than approximately 20% of the total weight of the remaining material.
In illustrative embodiments, an uncured binder may consist of a colorless, white, off-white, ocher or yellow to brown sticky substance that is at least partially water-soluble. As used herein, the term cured binder describes the polymeric curing product of the uncured binder composition. The cured binder may have a characteristic brown or black color. Although it is described as brown or black, another feature is that the binder tends to absorb light over a wide range of wavelengths. More specifically, there may be a higher absorbance at approximately 420 nm. As the polymer is extensively cross-linked, the cured binder is substantially insoluble. The binder is predominantly insoluble in water, for example. As described in this document, the uncured binder provides sufficient bonding capacity to consolidate fibers; however, the cured binder provides robust long-term durability and physical properties usually associated with cross-linked polymers.
In illustrative embodiments, the binder reagents described in this document are soluble in water and the binder solution is a solution of the binder reagents in an aqueous solution. In one embodiment, a surfactant is included in the aqueous solution to increase the solubility or dispersibility of one or more binder reagents or additives. A surfactant can be added, for example, to the aqueous binder solution to increase the dispersibility of a particulate additive. In one embodiment, a surfactant is used to create an emulsion with a non-polar additive or with a binder reagent. In another embodiment, the binder solution 15 comprises approximately 0.01% to approximately 5% of surfactant by weight based on the weight of the binder solution.
In illustrative embodiments, the binder solutions described in this document can be applied to mineral fibers (sprayed on the mat, for example, or sprayed on fibers as they enter the forming region) during the production of insulating fiber products mineral. When the binder solution is in contact with the mineral fibers, the residual heat of the mineral fibers (note that glass fibers, for example, are produced from molten glass and therefore contain residual heat) and the flow of air through the product and / or around it will cause a portion of the water to evaporate from the binder solution. Removing the water leaves remaining components of the binder in the fibers in the form of a viscous or semi-viscous mixture coating with a high solids content. This high solids viscous or semi-viscous mixture coating works as a binder. At this point, the mat has not yet been cured. In other words, the uncured binder works to bind the fibers to the mat.
In addition, it should be understood that the uncured binders described above can be cured. The process of making a cured insulating product, for example, can include a subsequent step in which heat is applied in order to cause a chemical reaction in the uncured binder composition. In the case of the manufacture of fiberglass insulating products, for example, after the binder solution has been applied to the fibers and dehydrated, the uncured insulating product can be transferred to a curing oven. In the curing oven, the uncured insulating product is heated (at a temperature of approximately 300 ° F to approximately 600 ° F [at a temperature of approximately 150 ° C to approximately 320 ° C]) producing the curing of the binder. The cured binder is a formless aldehyde and water resistant binder that binds the glass fibers of the insulating product together. Note that drying and thermal curing can occur in sequence, simultaneously, contemporaneously or concurrently.
In illustrative embodiments, an uncured fibrous product comprises from approximately 3% to approximately 40% of dry binder solids (total uncured solids by weight). In one embodiment, the uncured fibrous product comprises between approximately 5% and approximately 25% of dry binder solids. In another embodiment, the uncured fibrous product comprises approximately 50% to approximately 97% of fibers by weight.
As already mentioned here with respect to a binder on mineral fibers, a cured binder is the product of curing binder reagents. The term cured indicates that the binder has been exposed to conditions such that a chemical change has been triggered. Examples of these chemical changes include, but are not limited to, (i) covalent bonding, (ii) hydrogen bonding of the binder components, and (iii) chemical crosslinking of the polymers and / or oligomers in the binder. These changes can increase the binder's durability and solvent resistance compared to uncured binder. Curing of a binder can result in the formation of heat-treated material. In addition, a cured binder can result in increased adhesion between the material in a collection when compared to an uncured binder. Curing can be initiated by heat, for example, by microwave radiation and / or by conditions that initiate one or more of the chemical changes mentioned above. Although not limited to a specific theory, the cure can include the reaction of the carbohydrate and the nucleophile in a nucleophilic addition reaction or in a nucleophilic addition-elimination reaction.
In a situation where the chemical change in the binder results in the release of water, such as during polymerization and cross-linking, for example, a cure can be determined by the amount of water released above that which would occur by drying only. The techniques used to measure the amount of water released during drying compared to that which occurs when a binder is cured are well known in the art.
In illustrative embodiments, the nucleophile is a nitrogen-containing compound. In one embodiment, the cured binder composition comprises a nitrogen-containing polymer. In one embodiment, the polymer containing nitrogen is brown to black in color. Although not limited to a specific theory, the cured binder composition comprises a mixture of high molecular weight polymers. High molecular weight polymers can be characterized as being extremely cross-linked. In addition, high molecular weight polymers can be characterized as brown, complex furan ring and nitrogen containing polymers. The high molecular weight, as used herein, includes those polymers that have a molecular weight above 100,000 Daltons. Being made up of extremely crosslinked polymer chains, the molecular weight of the high molecular weight polymers described in the present is close to infinity. Consequently, the molecular weight of high molecular weight polymers can be a function of the mass and physical dimensions of the polymer being analyzed. A unitary sample of melanoidins, for example, which have a mass of 3 grams can be assumed to comprise a single polymeric molecule due to extensive cross-linking. Consequently, the molecular weight of the polymer would be approximately 1.8 x 1024 grams per mole (the product of the sample mass being Avogadro's number). As used herein, a high molecular weight polymer includes polymers having a molecular weight on the order of approximately 1 x 105 to approximately 1 x 1024 per mol.
Although not limited to a specific theory, it should be understood that high molecular weight polymers vary in structure according to reagents and preparation conditions. It is also known that high molecular weight polymers have a carbon-to-nitrogen ratio that increases with temperature and duration of heating. In addition, high molecular weight polymers have an unsaturated and aromatic saturated character. In one embodiment, high molecular weight polymers had a degree of unsaturation and aromaticity that increased with temperature (curing temperature) and with the duration of heating (curing time). High molecular weight polymers also contained the C-1 of these sugars incorporated as reactants in a variety of structures within the polymer. High molecular weight polymers can also contain carbonyl, carboxyl, amine, amide, pyrrole, indole, azomethine, ester, anhydride, ether, methyl and / or hydroxyl groups. Depending on the complexity of the structure, infrared spectroscopy can be useful in identifying one or more of these functional groups. Although not so classified in the present, those skilled in the art will note that the binder can be classified according to the existence of a specific bond present such as a polyester, polyether, polyamide etc.
Another way in which the binder is characterized is by analyzing the gaseous compounds produced during the pyrolysis of the cured binder. Gaseous pyrolysis of the cured binder within the scope of the present invention can yield approximately 0.5 to approximately 15% (per relative peak area) of one or more of the following compounds: 2-cyclopenten-l-one, 2,5-dimethyl -furan, furan, 3-methyl-2,5-furanedione, phenol, 2,3-dimethyl-2-cyclopenten-1-one, 2-methyl phenol, 4-methyl phenol, 2,4-dimethyl-phenol, phthalate dimethyl, octadecanoic acid or crucylamide. Analysis by pyrolysis-gas chromatography-mass spectrometry (Py GC-MS) conducted at 770 ° C of a binder sample prepared using hexamethylene diamine as the polyamine component shows pyridine and a series of components that are derived from pyrrole or pyridine (a methyl pyridine, a methyl pyrrole, dimethyl pyridines, a dimethyl pyrrole, an ethyl methyl pyrrole and other components containing N related to pyrrole). Another way in which the binder can be identified is if a solution containing the binder (or an extract solution) is capable of reducing Benedict's reagent. In one embodiment, a solution in contact with the binder or an aqueous extract of yours reduces Benedict's reagent.
One aspect of the present invention is that the binders described herein are environmentally friendly. In parallel with the advancing government regulation, the present invention describes a binder that can be prepared free of formic aldehyde. In addition, the chemical processes described herein are essentially free of formic aldehyde and phenol. In this sense neither formic aldehyde nor phenol is used as a reagent within the scope of the present invention. Although the two can be added, to obtain a binder with potentially useful properties, an aspect of the present invention consists of a binder that can be repaired free of these two reagents. In another aspect, the present binder composition can be produced without the use of volatile reagents. In one embodiment, the nucleophile and carbohydrate are both non-volatile reagents. As used herein, a volatile reagent is one that has a pressure value above 10 kPa at 20 ° C. Similarly, as used herein, a non-volatile reagent is one that has a vapor pressure less than approximately 120 kPa at 20 ° C. More specifically, and by way of example, the present binder can be manufactured without the addition of ammonia or an ammonia-releasing compound. In one embodiment, the nucleophile has a vapor pressure of less than approximately 0.5 kPa at 60 ° C.
Another favorable aspect from an environmental point of view is the fact that the primary reagents in the binder are carbohydrates. Carbohydrates are considered a renewable resource. However, the current state of the art mainly uses petroleum-based reagents for the manufacture of binder compositions. In another aspect, the binder is made by means of chemical reactions that can occur at lower temperatures than the comparable systems described in the prior art. For this reason, curing ovens and manufacturing equipment can be operated at lower temperatures, saving valuable resources. In an alternative and related way, the binder described herein is cured faster than the comparable binders currently used when subjected to similar curing temperatures. Consequently, by either approach, an aspect of the present invention is that the carbon footprint of a product formed using the binder described in this document can be substantially reduced compared to a comparable binder prepared in accordance with with the current state of the art, such as, for example, a product based on hay / formic aldehyde.
In addition to the environmental benefits, the present binder composition and the materials prepared with it can be produced in order to have performance characteristics equivalent to or superior to those of comparable binder systems, such as phenol / formic aldehyde binders, for example. In one aspect, a binder according to the present invention gives articles manufactured with it sufficient tensile strength to allow cutting and molding, fabrication, lamination and installation in OEM applications. In one aspect, a binder according to the present invention has a water-holding capacity (weather resistance) comparable to that of a phenol / formic aldehyde binder. Another performance characteristic that may be relevant to a specific application includes product emissions, its density, loss on ignition, thickness recovery, dust resistance, tensile strength, separation resistance, separation resistance durability, bonding strength , water absorption, hot surface performance, corrosivity on steel, flexural rigidity, hardness-rigidity, compressive strength, conditioned compressive strength, compressive module, conditioned compressive module and development of ignition smoke. One aspect of the present invention is that the cured binder extract has essentially a neutral pH, between a pH of 6 and 8, for example. Another aspect of the present invention consists in the fact that the present binder allows the manufacture of products that have relevant performance characteristics comparable to those of formic phenol-aldehyde binder compositions.
By way of illustration, in one embodiment, a binder according to the present invention has the advantage of producing essentially colorless aqueous extracts. This feature of the present invention makes the binder desirable in applications such as ceiling panels, furniture or office partitions, where the finished product can come into contact with water. A cured manufactured product produced with the present binder has excellent resistance to discoloration or bleeding after coming into contact with moisture or water. Furthermore, in such a modality, the water that comes in contact with the binder does not leave a residual color in other articles or components with which it can come in contact subsequently to contact with the binder. In one embodiment, for example, the binder can be used to bond glass fibers in an application to office partitions. To cover the bonded fiberglass composition there may be a light colored fabric. Advantageously, in one embodiment, the water that comes into contact with the fiberglass composition does not leave a colored residue on the fabric of the partition for the office to have dried.
In addition to the performance characteristics, the manufacturing processes and methods involving the binder described in this document also have a number of unexpected advantages when compared to those of the binders described above. In one aspect, as already described in relation to environmental benefits, the binder of the present invention can be manufactured without the use of extremely volatile reagents. Consequently, emission controls during manufacture are subject to lower charges. In addition, the efficiency of the reaction is increased, as the loss of reagents by evaporation is reduced. Consequently, an aspect of the present invention consists in the fact that the compounds used in this document are substantially non-volatile, therefore the steps that must be reduced are reduced. taken to mitigate undesirable emissions.
According to another aspect, the reagents that react to form a binder are slow to react so that a single step / single binder system can be used. According to this aspect, the reactive compounds have a sufficiently slow reaction so that they can be added to a single reagent solution and be stored for a reasonable period of time during which they can be applied to a product using a distribution system. This contrasts with those binder systems that react at low temperatures and that result in insoluble reaction products within the binder solution delivery systems. As used at present, a reasonable period of time for storage without substantial polymer precipitation (> 5%) is two weeks.
Another aspect of the present invention is the fact that, although the binder is sufficiently non-reactive under ambient temperature conditions that facilitates a single vessel approach, it is sufficiently reactive at elevated temperatures to produce the cure at very low temperatures and / or very short cure residence times. In a sense, the lower curing temperature reduces the risk of the insulating product burning without flame and / or producing fire in the pipes. As used at present, very low temperatures are characterized as being less than or equal to 120 ° C. As used at present, very short cure times are less than or equal to approximately 4 minutes.
In illustrative embodiments, the binder composition includes an acid or an acid salt to increase the shelf life of the uncured binder or binder solution. Although this acid is neither a reagent nor a catalyst, it can be included to slow or inhibit the binder reagents by preventing them from forming the binder while the uncured binder or binder solution is being kept in storage condition. A volatile acid or acid salt, for example, can be included in the binder solution or in the uncured binder that slows or inhibits the curing reaction under ambient conditions. However, the acid can be removed by heating the binder solution or uncured binder so that the acid is volatilized and the pH of the binder solution or uncured binder increases. In one embodiment, the binder composition includes an acid that prolongs shelf life. In another embodiment, the binder composition includes an acid molar ratio that prolongs the storage time for the nucleophile from approximately 1:20 to approximately 1: 1.
Another aspect of the present invention consists of a binder that has a cure rate, cycle time and curing temperature that match or exceed the cure rates that a comparable phenol / formic aldehyde type binder can exhibit within the scope of a comparable use. In this sense, the present binder can be used as a direct replacement for phenol / formic aldehyde resins in applications without any modification to the equipment. In addition, the binder present allows the curing temperature and curing times to be modified, so that both reaction temperatures and curing times can be reduced. This reduction has the effect of reducing the energy consumption of the process as a whole and reduces the environmental impact of manufacturing the product. In addition, lower curing temperatures have the added effect of increasing the safety of the manufacturing process. Another effect of lower curing temperatures is to reduce the risk of flameless combustion or fire.
In the manufacture of insulating products, the heat released by the exothermic curing reaction can result in the product self-heating. Self-heating is typically trouble-free as long as the heat dissipates from the product. However, if the heat increases the temperature of the product to a point where oxidative processes are initiated, self-heating can cause significant damage to the product. Flameless combustion, for example, or oxidation can occur when the temperature of the insulating product exceeds approximately 425 ° F (210 ° C). At these temperatures, exothermic combustion or oxidation processes promote the continuation of self-heating and the binder can be destroyed. In addition, the temperature can rise to a point where it is possible to fuse or devitrify the glass fibers. This not only damages the structure and value of the insulating product, but can also create a fire hazard.
Another aspect of the present invention is that the binder system is essentially non-corrosive with or without the addition of corrosion inhibitors. In addition, the binder system does not require the addition of any organic or inorganic acid or its salt as a catalyst or as an active ingredient. Consequently, an aspect of the present binder is that it can be produced essentially free of acid. In addition, the binder can be manufactured in entirely alkaline conditions. As used herein, the term acid includes those compounds that are mainly characterized by their acidic character such as multiprotic inorganic and organic acids (sulfuric acid and citric acid, for example). This reduces the demands on wear and maintenance of manufacturing equipment and increases the safety of workers.
In illustrative embodiments, a binder comprises a polymeric product of a carbohydrate reagent and a nucleophile. As used herein, the term carbohydrate reagent refers to a monosaccharide, a disaccharide, a polysaccharide, or a product of their reaction. In one embodiment, the carbohydrate reagent can be a reducing sugar. As used in the present reducing sugar, it indicates one or more sugars that contain aldehyde groups, or that can be isomerized, that is, tautomerized to contain aldehyde groups, and these groups can be oxidized with Cu + 2, for example, to produce carboxylic acids. It should also be noted that any carbohydrate reagent can be optionally substituted, with hydroxy, halo, alkyl, alkoxy etc., for example, and the like. It should further be appreciated that in any such carbohydrate reagent, one or more chiral centers are present, and that the two possible optical isomers at each chiral center are claimed in the invention described herein. In addition, it should be understood that various mixtures, including racemic mixtures or other diastereoisomeric mixtures of various optical isomers of any such carbohydrate reagent, as well as several geometric isomers thereof, may be used in one or more modalities described in this document. Although non-reducing sugars, sucrose, for example, may not be preferable, it may still be useful within the scope of the present invention for an in situ conversion to a reducing sugar (ie conversion of sucrose to inverted sugar is a method known in the art). technical). In addition, it should also be understood that a monosaccharide, disaccharide or polysaccharide can be partially reacted with a precursor to form a carbohydrate reaction product. Insofar as the carbohydrate reaction product is derived from a monosaccharide, disaccharide, or polysaccharide and retains a reactivity analogous to the nucleophile to form reaction products analogous to that of a monosaccharide, disaccharide, or polysaccharide with a nucleophile, the carbohydrate reaction product falls under the term carbohydrate reagent.
In one aspect, any carbohydrate reagent must be sufficiently non-volatile to maximize its ability to remain available for reaction with the nucleophile. The carbohydrate reagent can be a monosaccharide in the form of an aldose or ketosis, including a triosis, a tetrose, a pentose, a hexose or a heptose; or a polysaccharide; or combinations of them. When a triosis serves as the carbohydrate reagent, for example, or is used in combination with other reducing sugars and / or a polysaccharide, an aldotriose sugar or a ketotriose sugar, such as glycolic aldehyde and dihydroxy-acetone, can be used, respectively. When tetrose serves as a carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, aldotetrosis sugars, such as erythrosis and threose, can be used; and ketotetrosis sugars such as erythrulose. When a pentose serves as the carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, aldopentose sugars, such as ribose, arabinose, xylose and lixose, can be used; and ketopentose sugars, such as ribulose, arabulose, xylulose and lixulose. When a hexose serves as a carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, aldohexose sugars, such as glucose (ie, dextrose), mannose, galactose, alose, altrose, thamosis, gulose and idose, and ketohexoses sugars such as fructose, psychosis, sorbose and tagatose. When a heptosis serves as the carbohydrate reagent, or is used in combination with other reducing sugars and / or a polysaccharide, a keto-heptose sugar, such as sedo-heptulose, can be used. Other stereoisomers of each carbohydrate reagent not known to occur naturally are also claimed to be useful in the preparation of the binder compositions as described herein. In one embodiment, the carbohydrate reagent is high fructose corn syrup.
In illustrative embodiments, the carbohydrate reagent is a polysaccharide. In one embodiment, the carbohydrate reagent is a polysaccharide with a low degree of polymerization. In one embodiment, the polysaccharide consists of molasses, starch, cellulose hydrolysates, or mixtures thereof. In one embodiment, the carbohydrate reagent is a starch hydrolyzate, a maltodextrin, or a mixture thereof. Although high polymerization carbohydrates may not be preferable, they can nevertheless be useful within the scope of the present invention by depolymerization in situ (i.e., depolymerization by means of ammonization at elevated temperatures in a method known in the art).
In addition, the carbohydrate reagent can be used in combination with a polyhydroxylated non-carbohydrate reagent. Examples of polyhydroxylated non-carbohydrate reagents that can be used in combination with the carbohydrate reagent include, but are not limited to, trimethylolpropanol, glycerol, pentaerythritol, poly (vinyl alcohol), partially hydrolyzed poly (vinyl acetate) poly (vinyl acetate ) fully hydrolyzed and its mixtures. In one aspect, the non-carbohydrate reagent is sufficiently non-volatile to maximize its ability to remain available for reaction with a monomeric or polymeric polyamine. It should be noted that the hydrophobic character of the polyhydroxylated non-carbohydrate reagent may be a factor in determining the physical properties of a binder prepared in the manner described in this document.
As used in this document, a nucleophile is a reagent that forms a bond to its reaction partner (the electrophile) by donating the two bonding electrons. As used in the present, an electrophile is a conductor that forms a bond to its reaction partner (the nucleophile) by accepting the two bonding electrons from its reaction partner. By way of illustration, the electrophile is the carbohydrate described in this document. More specifically, the electrophilic group is the carbon associated with the form of aldose or ketosis of the carbohydrate. Glucose C-1, for example, is electropositive due to aldose functionality and reacts with a nucleophile of the present invention. In another example C-2 fructose is electropositive due to the functionality of ketosis reacts with a nucleophile of the present invention. Although it is described as an electrophile in its initial interaction with the nucleophile, those skilled in the art will note that the carbohydrate is not limited to acting only as an electrophile within the scope of the reactions that may occur. The hydroxyl groups of the carbohydrate, for example, can act as a nucleophile, depending on the presence of a reactive nucleophile. In addition, although the initial reaction between the nucleophile and the carbohydrate may classify the carbohydrate as an electrophile, the product of that reaction can have both nucleophilic and electrophilic functionality in later reactions.
In illustrative embodiments, the nucleophile is sufficient nucleophilic to react with a carbohydrate in the form of an aldose or ketosis in a solution that has a pH as described herein and at a temperature described herein. In one embodiment, the nucleophile includes a cationic stabilization portion. As used herein, a cationic stabilization moiety is a chemical group in the nucleophile that stabilizes the cation that forms after the nucleophilic attack. A nucleophile within the scope of the present invention, for example, is a diamine. After the nucleophilic attack of a carbonyl by a primary amine, a cation of a Schiff base is formed. Although the first amine of the diamine acts in the role of a nucleophile, the second amine acts in the role of a cationic stabilization moiety as it stabilizes the cation of the Schiff base. A further rearrangement of the Schiff base cation in the form of enol or keto is known to occur spontaneously. The cation that forms after the nucleophilic attack is stabilized in an analogous manner (as well as the Schiff base) by the structure of the nucleophile. In another aspect, the structure of the nucleophile accelerates the rearrangement by stabilizing the positive charge that is acquired while the compound is in the form of a cation that is formed by nucleophilic attack.
It was found that this spontaneous reaction is further facilitated by dehydration, as the rate was increased in dehydrated samples. It is believed that the importance of the stabilizing portion has not been discussed in the prior art within the scope of the present invention, since the enhanced effect of using a nucleophile of the present invention has not been previously disclosed. Consequently, an aspect of the present invention is that the nucleophile is of a type that provides stability to a cation of a nucleophilic base during subsequent rearrangement. In another aspect, the nucleophile is of a type that provides stability to a cation of a nucleophilic base during subsequent rearrangement while in a substantially dry state.
In illustrative embodiments, the nucleophile is Ri-Q-R2, where Q is alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which is optionally substituted, Ri is a nucleophilic moiety and R2 is the stabilizing moiety. In one embodiment, Ri is selected from the group consisting of an amine group, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl and a alkoxide. In another embodiment, R2 is selected from the group consisting of an amine group, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol).
In one embodiment, the nucleophile is a primary amine. As used herein, a primary amine is an organic compound that has one or more primary amine groups. Within the given scope, the term primary amine includes those compounds that can be modified in situ or isomerized to generate a compound that has one or more primary amine groups. In one embodiment, the primary amine may consist of a molecule that has the formula H2N-QR where Q is an alkyl, heteroalkyl, cycloalkyl, or cycloheteroalkyl group, each of which can be optionally substituted and R includes a cationic stabilization portion selected from the group consisting of an amine group, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol).
In one embodiment, Q is an alkyl selected from the group consisting of C2-C24 In another embodiment, Q is an alkyl selected from the group consisting of C2-C8. In another embodiment Q is an alkyl selected from the group consisting of C3-C7. In another embodiment, Q is C6 alkyl. In one embodiment, Q is selected from the group consisting of cyclohexyl, cyclopentyl or cyclobutyl. In another embodiment, Q is benzyl. In one embodiment, R1-Q-R2 is 2- [(2-aminoethyl) amino] ethanol. In another embodiment of Ri-Q-R2, each of Ri and R2 is thiol.
In one embodiment, Ri is an amino group. In another embodiment of the above, R2 is an amine, an amide, an imine or an imide group. In another embodiment of the above, R2 is an amino group.
As used herein, the term "alkyl" includes a chain of carbon atoms, which is optionally branched. As used herein, the terms "alkenyl" and "alkynyl" include a carbon atom chain that is optionally branched and includes at least one double or triple bond, respectively. It should be understood that alkynyl may also include one or more double bonds. It should be understood that alkyl is advantageously of limited length, including Ci-C24, C1-C12, Ci-Cs, Ci-Cg and C1-C4. It should be understood that each of alkenyl and / or alkynyl can advantageously be of limited length including C2-C24, C2-C12, C2-C8, C2-Cg and C2-C4. It should be noted in this document that shorter alkyl, alkenyl and / or alkynyl groups can add a lower hydrophilic character to the compound and consequently will have a different reactivity in relation to the carbohydrate reagent and a different solubility in a binder solution.
As used herein, the term "cycloalkyl" includes a chain of carbon atoms that is optionally branched with at least a portion of the cyclical chain. It should be understood that cycloalkylalkyl is a subset of cycloalkyl. It must be understood that cycloalkyl may be polycyclic. Illustrative cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 2-methyl-cyclopropyl, cyclopentyl-2-yl, adamantyl, and the like. As used herein, the term "cycloalkenyl" includes a chain of carbon atoms, which is optionally branched and includes at least one double bond, with at least a portion of the cyclical chain. It must be understood that one or more double bonds may be found in the cyclical portion of cycloalkenyl and / or in the non-cyclical portion of cycloalkenyl. It must be understood that cycloalkenylalkyl and cycloalkylalkenyl are in turn subsets of cycloalkenyl. It must be understood that cycloalkyl may be polycyclic. Illustrative cycloalkenyls include, but are not limited to, cyclopentenyl, cyclohexyleneth-2-yl, cycloheptenyl-propenyl and the like. It should also be understood that it is advantageous that the chain-forming cycloalkyl and / or cycloalkenyl are of limited length including C3-C24, C3-C12, C3-C8, C3-C6 and C5-C6. It should be noted in this document that alkyl and / or alkenyl chains that form cycloalkyl and / or cycloalkenyls, respectively, can add less lipophilic character to the compound and consequently, they will behave differently.
As used herein, the term "heteroalkyl" includes a chain of atoms that includes both carbon and at least one heteroatom, and is optionally branched. Illustrative heteroatoms include nitrogen, oxygen and sulfur. In certain variations, illustrative heteroatoms also include phosphorus and selenium. As used herein the term "cycloheteroalkyl", which includes heterocyclyl and heterocycle, includes an atom chain that includes both carbon atoms and at least one heteroatom, such as heteroalkyl, and that is optionally branched, being at least one portion of the cyclical chain. Illustrative heteroatoms also include oxygen and sulfur. In certain variations, heteroatoms also include phosphorus and selenium. Illustrative cycloheteroalkyls include, but are not limited to, tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl and the like. The term "optionally substituted" as used herein includes the replacement of hydrogen atoms by other functional groups in the radical that is optionally substituted. Such other functional groups include by way of illustration, but without limitation, amino, hydroxyl, halo, thiol, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acids and their derivatives, carboxylic acids and their derivatives and the like . By way of illustration, any amino, hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and / or sulfonic acid is optionally substituted.
In illustrative embodiments, the nucleophile is a diamine, triamine, tetramine or pentamine. In one embodiment, the polyamine is a triamine selected from diethylene triamine, 1-piperazine-ethane-amine, or bis (hexamethylene) triamine. In another embodiment, the polyamine is a tetramine, triethylene-tetramine, for example. In another embodiment, the polyamine is a pentamine, tetraethylene pentamine, for example.
One aspect of the nucleophile is the fact that it may have a low steric impediment. Q is selected in such a way, for example, that the nucleophile has a low steric impediment. If Q is essentially linear, for example and has a length of at least three atoms, the nucleophilic portion and the stabilizing portion are sufficiently spaced apart so that the nucleophile is able to react with the electrophile.
Although it is not desired to be limited to any specific theory, the stabilization portion is so named because of the possibility of stabilizing an intermediate reaction as described in this document. However, in another aspect of the present invention, the stabilizing portion can also serve as a reagent within the scope of the present invention. For this reason, the rearrangement products that exist after the reaction between the nucleophilic portion and the carbohydrate can convert or return the stabilization portion to a group that reacts or is capable of reacting with another carbohydrate. Consequently, the stabilizing portion can convert or return to the form of a nucleophilic portion and react with the carbohydrate, naturally.
In illustrative embodiments, the group Q, as described in this document, can serve to isolate the two groups, such that Rx and R2 are not essentially affected by the chemical reactions that take place in the other position. For this reason, the group Q may or may not serve in the capacity of a stabilizing portion. According to this theory, the advantage gained by using a difunctional nucleophile can be attributed mainly to the fact that a single difunctional compound can form a crosslink between two carbohydrate compounds. As the two functional groups are linked through a group Q, by reaction of the two Ri and R2, the result is a product of higher molecular weight than if Ri and R2 were not linked through the group Q. For this reason, Ri and R2 can be selected from the group consisting of an amine group, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl, an alkoxide, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a hydrogen, a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol).
In illustrative modalities, the group Q is the type that allows chemical communication between Ri and R2 • Q can allow chemical communication, for example, by allowing resonance and polarity deviation from Ri to R2 • In other modalities, Q can have such a length that reactions in either Ri or R2 produce changes in the distribution of electrons in the other group (Ri or R2). In one embodiment, the nucleophile includes a stabilizing portion and a nucleophilic portion. In one embodiment, the nucleophilic portion is selected from the group consisting of an amine group, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxylate, a carboxylate, a hydroxyl and an alkoxide. In another embodiment, the cationic stabilization portion is selected from the group consisting of an amine group, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphone, a hydroxyl, a hydrogen , a sulfone, a sulfo, a sulfinyl and a sulfhydryl (thiol).
In one embodiment, a nucleophile can include a polymeric polyamine. Polymeric polyamines, for example, which fall within the scope of the present invention include chitosan, polylysine, polyethylene imine, poly (N-vinyl-N-methyl amine), polyaminostyrene and polyvinylamines. In one embodiment, the polyamine comprises a polyvinyl amine. As used herein, polyvinylamine can be a homopolymer or a copolymer.
While not limited to a specific theory, an aspect of the present invention is that the primary amine and the carbohydrate reagent are Maillard reagents that react to form a melanoidin product. Figure 1 shows a scheme of a Maillard reaction that results in the production of melanoidins. In its initial phase, a Maillard reaction involves a carbohydrate reagent, a reducing sugar, for example, (note that the carbohydrate reagent may come from a substance capable of producing a reducing sugar under the conditions of the Maillard reaction) . The reaction also involves condensing the carbohydrate reagent (a reducing sugar, for example) with an amine reagent, that is, a compound that has an amino group. In other words, the carbohydrate reagent and the amine reagent are the melanoidin reagents for a Maillard reaction. The condensation of these two constituents produces a N-substituted glycosylamine. For a more detailed description of the Maillard reaction see Hodge, J. E. Chemistry of Browning Reactions in Model Systems, J. Agric. Food Chem. 1953, I, 928-943, the content of which is incorporated into this document as a reference. The literature on Maillard reactions focuses on melanoidins produced from amino acids. The present invention can be distinguished from these references by the fact that nucleophiles within the scope of the present invention also include a stabilizing portion. Common amino acids that are considered within the scope of the present invention include asparagine, glutamine, histidine, lysine and arginine.
Without wishing to be surrounded by theory, the covalent reaction between the nucleophile and the carbohydrate reagent will now be described more specifically. As described in this document, the path of the present reaction is distinct from those taught in the prior art for the following reasons: (1) the present reaction can occur completely at a basic pH, (2) the nucleophile is difunctional, having a nucleophilic portion and a stabilization portion, (3) the nucleophile, due to its difunctionality or due to some other unknown phenomenon, presents a lower activation energy within the scope of the reaction which results in an unexpected increase in the reaction rate and / or a reduction in temperature to which the reaction will occur.
In illustrative embodiments, the first step in the formation of high molecular weight polymers from the nucleophile and a carbohydrate reagent is the condensation of the carbohydrate reagent and the nucleophile. The evidence indicates that the conditions described in this document are especially suitable for bringing this reaction to an end. First, it is believed that the alkalinity of the binder solution moves the condensation. It has been shown, for example, that sugars and nucleophiles such as amines undergo a brown color in aqueous solution proportional to the basic intensity of the amines employed or the pH of the solution. In this example, it is believed that the N-substituted glycosylamines remain without dissociating in aqueous solutions to a considerable extent. Thus, the irreversible transformations that molecules that have not dissociated undergo must be taken into account. Although it is known that the condensation reaction is reversible, we have found that this reaction can still be carried out, according to the principle of Le Chatelier for dehydrating the binder solution. For this reason, it was established that initially a constituent of the uncured binder composition consisted of the condensation products of the nucleophile and carbohydrate.
The second step in converting the binder reagents into high molecular weight polymeric products can be a rearrangement. An exemplary rearrangement is shown in schematic form of an Amadori rearrangement in Figure 2. With reference to Figure 2, the N-glycosylated derivatives of the representative amines are in equilibrium with the cation of a Schiff base. Although this balance favors N-glycosylamine, a subsequent rearrangement of the Schiff base cation in the form of enol or keto is known to occur spontaneously. This spontaneous reaction was found to be further facilitated by dehydration as the rate increased in dehydrated samples. One aspect of the present invention is that the structure of a nucleophile specifically accelerates this rearrangement by stabilizing the positive charge that is acquired while the compound is in the form of a Schiff base cation. It is believed that this stabilizing effect has not been discussed in the prior art or in the literature as the enhanced effect of using a nucleophile, since such a fact within the scope of the present invention has not been previously disclosed. Consequently, an aspect of the present invention is that the nucleophile is of a type that provides stability to a cationic base during rearrangement. In another aspect, the nucleophile is of a type that provides stability to a cationic base during rearrangement while in a substantially dry state.
Another aspect of the present invention is that the structure of the carbohydrate is also believed to have an influence on the rearrangement kinetics. More specifically, it is known that when the C-2 hydroxyl group of a crystalline glycosylamine with N substituted had not been substituted, the compound slowly transformed during storage in the rearrangement product. However, if the hydroxyl group at C-2 were replaced, then the rearrangement would be substantially inhibited. Consequently, an aspect of the present invention is that the carbohydrate of the present invention is not substituted in the hydroxyl group adjacent to the ketone or aldehyde.
In illustrative modalities, the molar ratio of the carbohydrate reagent to the nucleophile is in the range of approximately 1: 1 to approximately 30: 1. In another embodiment, the molar ratio of the carbohydrate reagent to the nucleophile is in the range of approximately 2: 1 to approximately 1: 1. In another embodiment, the molar ratio of the carbohydrate reagent to the nucleophile is in the range of approximately 3: 1 to approximately 6: 1. According to one aspect, the cure rate is a function of the molar ratio of the carbohydrate reagent to the primary polyamine. According to this function, it was established that as the molar ratio decreased, the cure rate increased; therefore, the curing time was reduced. Consequently, an aspect of the present invention consists in the fact that the curing time is directly related to the molar ratio of the carbohydrate reagent to the polyamine, as long as the other parameters are kept equivalent. In another aspect, the curing time of the binder is reduced to the curing time of a comparable binder composition of phenol / formic aldehyde when the molar ratio of the carbohydrate reagent to the nucleophile is approximately 6: 1. Consequently, in one embodiment, a binder according to the present invention has a cure rate that exceeds that of a comparable phenol / formic aldehyde binder system when the molar ratio of the carbohydrate reagent to the nucleotide is in the range of approximately 2 : 1 to approximately 6: 1.
Another aspect of the reaction, as described in this document, is the fact that the aqueous reagent solution (which can be dehydrated and used as a binder) initially has an alkaline pH. One aspect of the present invention is that the alkaline binder solution is less corrosive to the metal than the acidic solution. Consequently, a feature of the present invention that overcomes a substantial barrier to industry is that the binder described in this document has a low corrosivity to the manufacturing equipment that can be used to produce materials that include the present binder due to the alkaline composition of the binder. A distinguishing feature of the present invention with respect to other carbohydrate binder systems (as in U.S. published application No. 2007/0027283, for example), is that the reaction does not necessarily follow an acidic path. In fact, an aspect of the present invention is that the uncured binder may have an alkaline pH throughout the course of the chemical reaction that leads to the formation of the cured binder. For this reason, the uncured binder throughout its use and storage does not present any risk of corrosion. In illustrative embodiments, an aqueous extract of the cured binder has a pH in the range of approximately 5 to approximately 9. In addition, an aqueous extract of the polymeric product is essentially colorless.
In illustrative embodiments, a method of making a collection of material bound with a polymeric binder comprises preparing a solution containing the reagents for the production of the polymeric binder and a solvent, including the reagents a carbohydrate reagent and a nucleophile; arrange the solution on the material collection; volatilize the solvent to form an uncured product and subject the uncured product to conditions that cause the carbohydrate reagent and the nucleophile to polymerize to form the polymeric binder.
In illustrative modalities, the material collection includes insulating fibers. In one embodiment, a fibrous insulating product is described that includes insulating fibers and a binder. As used herein, the term "insulating fiber" indicates heat resistant fibers suitable for withstanding high temperatures. Examples of such fibers include, but are not limited to, mineral fibers (glass fibers, slag wool fibers, and rock wool fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyester fibers and rayon fibers. By way of illustration, such fibers are not substantially affected by exposure to temperatures above approximately 120 ° C. In one embodiment, the insulating fibers are glass fibers. In another embodiment, mineral fibers are present in a range of approximately 70% to approximately 99% by weight.
In illustrative modalities, the material collection includes cellulosic fibers. Cellulosic fibers, for example, can consist of wood chips, sawdust, wood pulp or crushed wood. In another embodiment, cellulosic fibers can be other natural fibers such as jute, linen, hemp and straw. The binder described in this document can be used instead of the binder described in published PCT application WO 2008/089847, which is integrally incorporated into this document by way of reference. In one embodiment, a composite wood board comprising wood particles and a binder is described. In another embodiment, the composite wood board is free of formic aldehyde. In one embodiment, the composite glass board has a range of nominal thicknesses from 6 mm to 13 mm, and has an elastic modulus (MOE) of at least approximately 1050 N / mm2, a flexural strength (MOR) of at least least approximately 7 N / mm2, and an internal bonding force (IB) of at least 0.20 N / mm2. In another embodiment, the composite wood board has a range of nominal thicknesses from 6 mm to 13 mm, and has a flexural strength (MOR) of at least approximately 12.5 N / mm2 and an internal bonding strength ( IB) of at least 0.28 N / mm2. In another embodiment, the composite wood board has a range of nominal thicknesses from 6 mm to 13 mm, and has an elasticity modulus (MOE) of at least approximately 1800 N / mm2, a flexural strength (MOR) of at least 133N / mm2, and an internal bonding force (IB) of at least 0.40 N / mm2. In another embodiment, the composite wood board has an elasticity modulus (MOE) of at least approximately 1800 N / mm2. In another embodiment, the composite wood board has an elasticity modulus (MOE) of at least approximately 2500 N / mm2. In another embodiment, the composite wood board has a flexural strength (MOR) of at least approximately 14 N / mm2. In yet another modality, the composite wood board has a flexural strength (MOR) of at least approximately 18 N / mm2. In one embodiment, the composite wood board has an internal bonding strength (IB) of at least 0.28 N / mm2. In another embodiment, the composite wood board has an internal bond strength (IB) of at least 0.4 N / mm2. In yet another embodiment, the composite wood board swells by less than approximately 12% or approximately 12% as measured by a change in thickness, after 24 hours in water at 20 ° C. In another embodiment, the composite wood board absorbs water after 24 hours in water at 20 ° C up to approximately 40% or even less than approximately 40%.
In illustrative embodiments, the composite wood board is a board of wood particles, a board of oriented filaments or a board of medium density fibers. In one embodiment, the binder constitutes approximately 8% to approximately 18% by weight (dry resin weight for dry wood particle weight) of the composite wood board. In another embodiment, the composite wood board also comprises a wax. In yet another embodiment, the composite wood board comprises approximately 0.1% to approximately 2% wax by weight of the composite wood board. In illustrative modalities, the method of producing a collection of material bound with a polymeric binder can also include the preparation of a solution by adding an amount of a carbohydrate reagent and an amount of a nucleophile so that the molar ratio is in the range from approximately 2: 1 to approximately 10: 1. In one embodiment, the preparation of the solution includes the addition of carbohydrate and polyamine reagent to an aqueous solution. In another embodiment, the preparation of the solution includes adjusting the pH of the solution to cover a range between approximately 8 and approximately 12. In in another embodiment, the method of preparing a collection of material bonded with a polymeric binder can further comprise packaging the uncured product in a packaging material suitable for storage.
In illustrative embodiments, the present invention relates to a composition comprising a collection of material and a binder, the binder comprising polymeric products from a reaction between a carbohydrate reagent and a nucleophile, the polymeric products being substantially insoluble in water. In one embodiment, the material collection includes mineral fibers, aramid fibers, ceramic fibers, metallic fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, or cellulosic fibers. Cellulosic fibers, for example, can include wood chips, sawdust, wood pulp and / or crushed wood. In one embodiment, the material collection includes sand or other particulate inorganic material. In one embodiment, the material collection consists of coal particles. In one embodiment, the carbohydrate reagent is selected from the group consisting of dextrose, xylose fructose, dihydroxy-acetone and their mixtures. In one embodiment, the nucleophile is R1-Q ~ R2, in I Q is alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, each of which is optionally substituted, Ri is a nucleophilic moiety and R2 is a stabilizing moiety.
In another embodiment, the composition further comprises a compound containing silicon. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized alkylsilyl ether, such as, for example, an amino functionalized alkylsilyl ether. In one embodiment, for example, the silicon-containing compound can be gamma-aminopropyltriethoxysilane, gamma-glycidoxyppropyltrimethoxysilane or amino-ethylaminopropyl-trimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound can be an aminofunctional oligomeric siloxane. In another embodiment, the composition comprises a corrosion inhibitor selected from the group consisting of anti-dust oil, monoammonium phosphate, melamine sodium metasilicate pentahydrate, tin (II) oxalate and a liquid hydrogenated methyl silicone emulsion.
In other illustrative modalities, the binder can be placed on a collection of fibers, substantially dehydrated, conditioned, and then stored or sold to third parties. It may refer to an uncured product sold to a third party for use in other manufacturing processes as "shipped out uncured". It can refer to an uncured product stored for use in other manufacturing processes as "preserved in the uncured facility". When sold or stored, this type of product is packaged in suitable containers or bags.
In illustrative embodiments, a conditioned uncured fibrous product comprises an uncured binder composition and a collection of fibers, with (i) the uncured binder composition being in contact with the fiber collection consolidating the fiber collection and (ii) the Uncured binder composition in contact with the fiber collection is packaged in a suitable packing material. In one embodiment, the amount of moisture in the uncured binder composition can range from approximately 1% to approximately 15% by weight based on the total weight of the product. In yet another embodiment, the suitable packaging material may be able to maintain the amount of moisture in the uncured binder composition up to approximately 20% of the original moisture level over a period of one week at room temperature and pressure environment. In one embodiment, the conditioned uncured fibrous product comprises from approximately 3% to approximately 30% by weight of the uncured agglutinating composition based on the weight of the conditioned uncured fibrous product without regard to the weight of the suitable conditioning material. In one embodiment, the conditioned uncured fibrous product comprises approximately 60 to approximately 97% by weight of fibers based on the weight of the insulating uncured fibrous product without regard to the weight of the suitable packaging material.
One aspect of the present invention is the fact that the binder described in this document is surprisingly useful in applications for both uncured product shipped outside and in a product preserved in the uncured installation. More specifically, uncured products sent out and uncured products preserved in the facility are provided with an uncured binder so that curing can take place at a later time and at another location. In the case of uncured products shipped abroad, the curing temperature and curing time are properties of the product that are of great importance to customers. More specifically, curing temperatures must be low enough that the product can be cured using existing equipment. In addition, the curing time must be short enough that the operating cycle time for curing the products remains short. Within this industry, manufacturing equipment and acceptable operating cycle times have been established for uncured products comprising phenol / formic aldehyde resins. Therefore, low curing temperatures are those curing temperatures suitable for curing a comparable phenol / formic aldehyde product. Similarly, sufficiently short circulation times are those operating cycle times that would be routine for curing a comparable phenol / formic aldehyde product. Those skilled in the art will note that neither cure time nor cure temperature can be presented as defined quantities due to the fact that specific applications can have dramatically different parameters. However, it is well understood that the curing time and curing temperatures of a model system provide sufficiently representative information with respect to the kinetics of the underlying chemical curing reaction, so that reliable predictions of the binder performance can be made in the various applications.
In illustrative embodiments, the curing time and curing temperature of the binder are the same as those of the comparable phenol / formic aldehyde binder composition or less than hers. In one embodiment, the curing time of the binder is less than the curing time of a comparable phenol / formic aldehyde binder composition. In another embodiment, the curing temperature of the binder is lower than the curing temperature of a comparable binder composition of phenol / formic aldehyde. As used herein, a comparable phenol / formic aldehyde binder composition is as described in accordance with U.S. Patent No. 6,638,882, which is integrally incorporated herein by reference.
As will be discussed below, several additives can be incorporated into the binder composition. These additives impart additional desirable characteristics to the binders of the present invention. The binder can include, for example, a coupling agent containing silicon. Many silicon-containing coupling agents are commercially available from Dow-Corning Corporation, Evonik Industries and Momentive Performance Materials. By way of illustration, the silicon-containing coupling agent includes compounds such as silylethers and alkylsilyl ethers, each of which may optionally be substituted, such as with halogen, alkoxy, amino and the like. In a variation, the silicon-containing compound is an amino substituted silane, such as y-aminopropyltriethoxy silane (SILQUEST — 1101; Momentive Performance Materials, Corporate Headquarters: 22 Corporate
Woods Boulevard, Albany, NY 12211 USA). In another variation the silicon-containing compound is an amino substituted silane, such as, for example, aminoethylaminopropyl-trimethoxy silane (Dow Z-6020; Dow Chemical, Midland, MI; USA). In another variation, the silicon-containing compound is y-glycidoxy-propyltrimethoxy silane (SILQUEST A-187; Momentive). In yet another variation, the silicon-containing compound is an aminofunctional oligomeric siloxane (HYDROSIL 2627, Evonik Industries, 379 Interpace Pkwy, Parsippany, NJ 07054).
Silicon-containing coupling agents are typically present in the binder in the range of approximately 0.1 percent to approximately 1 weight percent based on dissolved binder solids (i.e., approximately 0.05% to approximately 3% with based on the weight of solids added to the aqueous solution). In one application, one or more of these silicon-containing compounds can be added to the aqueous binder solution. The binder is then applied to the material to be bonded. Then the binder can be cured, if desired. These silicon-containing compounds increase the ability of the binder to adhere to the material on which the binder is placed, such as glass fibers. Increasing the binder's ability to adhere to the substance increases, for example, its ability to produce or promote cohesion in a non-agglomerated or loosely agglomerated substance (s).
In another illustrative embodiment, a binder of the present invention can include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit corrosion or wear of a substance, such as a metal, caused by chemical decomposition caused by an acid. When a corrosion inhibitor is included in a binder of the present invention, the corrosivity of the binder is reduced in comparison to the corrosiveness of the binder without the inhibitor present. In one embodiment, these corrosion inhibitors can be used to reduce the corrosivity of the glass fiber-containing compositions described herein. By way of illustration, corrosion inhibitors include one or more of the following, an anti-dust oil, or a monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and / or liquid hydrogenated silicone emulsion. of methyl. When included in a binder of the present invention, corrosion inhibitors are typically present in the binder in the range of approximately 0.5 percent to approximately 2 percent by weight based on the dissolved solids in the binder. One aspect of the present invention is that the need for corrosion inhibiting additives is greatly reduced by the alkalinity of the binder solution and the substantially dehydrated, uncured binder. In one embodiment, the binder is free from corrosion inhibitors and the corrosivity of the binder solution is within acceptable limits.
In illustrative embodiments, the binder may also include a non-aqueous humidifier. The non-aqueous humidifier may include one or more polyethers. The non-aqueous humidifier may include an ethylene oxide condensate or a propylene oxide condensate having straight or branched chain and alkyl alkyl groups. In one embodiment the non-aqueous humidifier includes a polyethylene glycol, a polypropylene glycol ether, a thioether, a polyoxyalkylene glycol (such as Jeffox TP400®), a dipropylene glycol and / or a polypropylene glycol (such as Pluriol P425® or Pluriol 2000 ®). In one embodiment, the non-aqueous humidifier comprises a polyoxyalkylene glycol or a polypropylene glycol. In another embodiment, the non-aqueous humidifier includes a compound based on a polyhydroxy compound (such as a fully or partially esterified polyhydroxy compound). In another embodiment, the non-aqueous humidifier includes a glycerin-based polyhydroxy, a propylene glycol, an ethylene glycol, a glycerin acetate, a sorbitol, a xylitol or a maltitol.
In another embodiment, the non-aqueous humidifier includes other compounds that have a multiplicity of hydroxyl groups based on tetrahydrofuran, a caprolactone and / or alkylphenoxypoli (ethyleneoxy) ethanols having alkyl groups containing from 7 to 18 carbon atoms and having approximately 4 to approximately 240 ethylenoxy units. The non-aqueous humidifier, for example, can include a heptylphenoxypoli (ethylenoxy) ethanol and / or a nonylphenoxypoli (ethylenoxy) ethanol. In another embodiment, the non-aqueous humidifier includes a polyoxyalkylene derivative of hexitol such as a sorbitan, sorbide, mannan, and / or a mannan. In another embodiment, the non-aqueous humidifier may include a partial long chain fatty acid ester, such as a polyoxyalkylene derivative of sorbitan monolaureate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate and / or sorbitan trioleate.
In illustrative embodiments, the non-aqueous humidifier includes a condensate of ethylene oxide with a hydrophobic base, the base being formed by the condensation of propylene oxide with propylene glycol. In one embodiment, the non-aqueous humidifier includes a sulfur-containing condensate, such as those prepared by condensing ethylene oxide with a higher alkyl mercaptan (such as nonil mercaptan, dodecyl mercaptan, tetradecyl mercaptan or alkylthiophenols that are approximately 6 to approximately 15 carbon atoms in the alkyl group). In another embodiment, the non-aqueous humidifier includes an ethylene oxide derivative of a long-chain carboxylic acid, such as lauric, myristic, palmitic or oleic acid. In another embodiment, the non-aqueous humidifier includes an ethylene oxide derivative of a long-chain alcohol such as octyl, decyl, lauryl or cetyl alcohol. In another embodiment, the non-aqueous humidifier includes a copolymer of ethylene oxide / tetrahydrofuran or a copolymer of ethylene oxide / propylene oxide.
The examples below illustrate specific modalities with additional details. These examples are given for purposes of illustration only and are not to be considered as limiting the invention or the inventive concept in any way to any specific physical configuration. EXAMPLES
Example 1: A solution of 50 g of dextrose (0.278 mol), 50 g of hexamethylene-diamine (0.431 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 11.9) was heated to the boiling point of the solution. A water-insoluble brown polymer was observed as a precipitate in the reaction vessel.
Example 2: From the solution above 50 g dextrose (0.278 mol), 50 g hexamethylene diamine (0.431 mol) dissolved in 566.6 deionized water (a 15% solids solution, pH 11.9), 2 g of the binder solution were applied to a filter pad which is placed on a Moisture Scale and heated for 15 minutes at 120 ° C. A brown water-insoluble polymer formed on the filter pad. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8.
Example 3: A solution of 85 g of dextrose (0.472 mol), 15 g of hexamethylene diamine (0.129 mol) dissolved in 566.6 g of deionized water (15% solids solution, pH 10.8) was prepared. 2 g of the binder solution was applied to a filter pad which is placed on a Moisture Scale and heated for 15 minutes at 140 ° C. A brown water-insoluble polymer formed on the filter pad. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8.
Example 4: A solution of 95 g of dextrose (0.528 mol), 5 g of hexamethylene diamine (0.043 mol) dissolved in 566.6 g of deionized water (15% solids solution) was prepared. 2 g of binder solution was applied to a filter pad which is placed on a humidity scale and heated for 15 minutes at 180 ° C. A slightly brown, water-insoluble polymer formed on the filter pad. An extraction of the cured filter pad using 100 g of deionized water is essentially colorless and has a pH of 6.8.
Comparative Example 1: A solution of 180 g of dextrose (1 mol) dissolved in 1020 g of deionized water (15% solids solution) was prepared. 2 g of the binder solution was applied to a filter pad which is placed on a humidity scale and heated for 15 minutes at 180 ° C. A water-insoluble polymer did not form on the filter pad. The resulting heat-treated binder was essentially totally water-soluble.
Curing Rate and Curing Time: Square fiberglass mats (13 "x 13" [33.02 cm x 33.02 cm]) with a weight of 44 g (corresponding to 34.5 g / ft2 [371, 35 g / m2]) were impregnated with a binder containing 15% solids. Excess binder is removed by vacuum suction, and the wet mat is dried for at least 12 hours at 90 ° F (32.22222222 ° C) in one (recirculation).
The dry mat is cut into four squares of the same dimensions. The squares are stacked on top of each other and at least one thermocouple connected to a recorder (i.e., oven m.o.l.e.) is placed in the middle of the stack between the 2nd. and the 3rd. layer.
A temperature controlled molding press is heated to 400 ° C (204 ° C). The sample with the prepared thermocouple is placed in the middle of the plate and compressed to a thickness of 5/8 "(1.5875 cm) for a predefined period of time (that is, 3.5 min, 4.0 min, 5, 0 min, 6.0 min, 15 min).
Each molded sample was evaluated for its degree of cure by testing the uniformity of surfaces, water retention and extract. A sample was considered cured when the surfaces are smooth without any "bumps", the sample does not noticeably weaken when immersed in water and no significant extract color is formed when the sample is immersed in water. The thermal profile of the sample center is measured during the molding cycle and is shown in Figure 3. Comparative Example 2: Phenol / formic aldehyde binder Composition based on dry solids: - 2.41 parts of ammonium sulphate - 1, 08 part of ammonia - 0.21 part of Silane A1101 - 96.3% pre-mixture of phenol resin / formic aldehyde: urea (70:30) Refer to Comparative Example 2 as Binder 1 in Figure 3. Comparative Example 3: Carbohydrate-Inorganic Acid Binder. Composition based on dry solids: - 81, 59 parts of dextrose - 17.09 parts of ammonium sulfate - 1 part ammonia - 0.3 part silane A1101 Refers to Comparative Example 2 as the Binder 2 in Figure 3. Example 5: Composition based on dry solids: - 80.94 parts of dextrose and ammonia solution (aqueous solution containing 2 moles / liter of dextrose and 2 moles / liter of ammonia) - 19.06 parts of hexamethylene diamine to example 5 as binder 4 in Figure 3.
It has been determined that the time required to achieve complete curing of a binder within the scope of the present invention is less than that of 3 comparative exemplary binder systems with various chemical characteristics. This model system illustrates the fact that the curing time, keeping the other variables constant, depends on the chemical characteristics of the binder system. The chemical characteristics of an illustrative binder composition within the scope of the present invention achieve more advantageous curing times compared to these other exemplary systems. The results are shown below:

Referring now to Figure 3, the characteristic temperature profile is shown for each of the binders 1, 2 and 4. It was observed that the temperature profile is characteristic for each binder. It was not established that the cure rate and cure time were not characteristic of the cure temperature profile. However, the cure temperature profile helps to understand and predict the cure rate and cure time. More specifically, Comparative Example 3 required a longer curing time and similarly the curing temperature profile required a maximum amount of time for asymptotic maximization. Similarly, Example 5 required the minimum amount of time for asymptotic maximization, and demonstrated the minimum cure time.
Effect of Reagent Carbohydrate: Polyamine Ratio on Curing Cycle Time. Wet State Mats (WLM) were prepared with varying ratios of dextrose monohydrate (DMH) to hexamethylene diamine (HMDA). The weight ratios tested include 75/25, 85/15 and 92/8, respectively. A 15% dextrose-HMDA binder was applied to 5 WLMs. The following binder compositions were prepared:

The mats are prepared in pieces of 13 / "x 13" (33.02 cm x 33.02 cm) with a thickness of 3/8 "(0.9525 cm) The press used to shape the mats is adjusted to 400 ° F (204.4444444 ° C). After being molded, the sample is approximately 5/8 "(1.5875 cm) thick. A temperature profile was first determined at 15 minute intervals. The next sample was compressed for 4 minutes: this is the time needed to cure a comparable binder composition of phenol / formic aldehyde (results not shown). The experiments were repeated with variable curing times until the minimum time required to cure each composition was determined. The extent to which each binder had been cured was determined based on weight. The following results were determined:

As described above, a comparable product based on hay / formic aldehyde (such as Comparative Example 2, for example) is cured with a cycle time of 4 minutes. In addition, the comparable carbohydrate binder (such as Comparative Example 3, for example) is cured over a 5 minute time cycle. These results indicate that a binder within the scope of the present invention with a reactive carbohydrate to primary polyamine ratio of 85/15 or less is cured at a rate comparable or faster than the product based on hay / formic aldehyde. Other experiments have shown that the curing temperature can be reduced in products that have a shorter curing time to obtain curing times equivalent to lower temperatures. The results obtained 5 satisfied in principle our expectations based on the Arrhenius equation.
In addition to these examples described in detail, the following examples have been given to ensure that the reactive carbohydrate and polyamine can comprise a wide range of alternatives.
Other Dextrose-Nucleophile Examples: Example 16: A suspension of 56, 80 g of deionized water, 7.15 g of dextrose monohydrate and 3.5 g of 1.12-diaminododecane was acidified with 11N HCl to a pH of 15 1.0, and was heated to 70 ° C with stirring resulting in a colorless transparent solution. The solution forms a water-insoluble thermoset polymer at 160 ° C (Test conditions: 2 g of binder solution are applied to a filter pad which is placed on a moisture balance. The filter pad is heated for 15 minutes at 160 ° C). An extract from the filter pad cured with 100 g of deionized water is essentially colorless. Example 17: A solution of 8.25 g of dextrose monohydrate and 2.50 g of 1,5-diamino-2-methylpentane (Dytek A Invista) dissolved in 56.08 g of deionized water forms a water-insoluble heat-cured polymer at 160 ° C. (Test condition: 2 g of binder solution is applied to a filter pad which is placed on a humidity scale. The filter pad is heated for 15 minutes at 160 ° C). An extract from the filter pad cured with 100 g of deionized water is essentially colorless. Example 18: A solution of 8.03 dextrose monohydrate and 2.70 g of N- (3-aminopropyl) -1,3-propane diamine dissolved in 56.08 g of deionized water forms a water-insoluble heat-corrected polymer at 200 ° C (Test condition: 2 g of binder solution is applied to a filter pad which is placed on a humidity scale. The filter pad is heated for 15 minutes at 200 ° C). An extract from the filter pad cured with 100 g of deionized water was slightly yellow in color. Example 19: A solution of 3 g of dextrose (0.016 mol) and 0.5 g of hexamethylene diamine (0.004 mol) dissolved in 9 ml of deionized water was prepared. This reaction mixture was heated at 100 ° C for 1 hour before 0.7 g of dithiothreitol (0.004 mol) was added to the mixture which was poured onto a filter pad, this filter pad being heated to 125 ° C. A brown water-insoluble polymer was formed on a filter pad. Example 20: A solution of 3 g of dextrose (0.016 mol), 0.5 g of hexamethylene diamine (0.004 mol) dissolved in 9 ml of deionized water was prepared. This reaction mixture was heated at 100 ° C for 1 hour before 0.52 g of butanedithiol (0.004 mol) was added to the mixture which was dripped onto a filter pad, this filter pad being heated to 125 ° C. A brown water-insoluble polymer was formed on the filter pad. Procedure for analyzing a sample of binder with gaseous pyrolysis. Approximately 10 g of a cured product that had the binder disposed on it is placed in a test tube, the tube is then heated to 1000 ° F (537.7777778 ° C) for 2.5 minutes when a sample is then extracted from the space higher and analyzed by gas chromatography / mass spectrometry (GC / MS) under the following conditions: Oven, 50 ° C for one minute - 10 ° C / minute to 300 ° C for 10 minutes; inlet, 280 ° C, without cracks; HP5 column 30 mm x 0.32 mm x 0.25 mm column flow, 1.11 mL / minute helium; 280 ° C MSD detector; injection volume, 1 mL; Detector mode, scan 34-700 amu; threshold, 50; and sample rate 22 scans / second A computer search of the mass spectrum of a chromatographic peak in the sample is conducted against the Wiley library of mass spectra. The best match is reported. A quality index (proximity to correspondence with the library spectra) ranging from 0 to 99 is generated. Only the identity of the peaks with the quality index above or equal to 90 is reported. The table below provides representative pyrolysis data that is expected from GC / MS analysis of gaseous compounds produced during the pyrolysis of a melanoidin-based binder composition.
Below is a list of the species observed in the pyrolysis gas chromatography / spectrometry (Py GC-MS) 5 of a binder sample prepared using hexamethylenediamine as the polyamine component. Pyrolysis was carried out at 200 ° C, 300 ° C and 770 ° C. The impression taking shows a significant peak that corresponds to acetic acid in the mass chromatogram both at 10 to 200 ° C and at 300 ° C, which was not observed in a sample produced using dextrose and ammonium sulfate (see Example Comparative 3), where the significant volatile fraction consisted of SO2, especially at 300 ° C. At 770 ° C, the observed peaks, in increasing order of retention time, were assigned as follows: A: Coelution of C5H10, C5H12, acetone, possibly low molecular weight acetic acid ester; B: C5H8 diene; C: C5H8 diene; D: probably a pentanol; E: CeHi2 - a methyl pentene; F: hexane; G: methylcyclopentane; H: a cyclohexadiene; I: CgHio - probably a methylcyclopentane; J: benzene; K: acetic acid; L: cyclohexene; M: probably nonanol; N: 2-methyl-3-pentanone; 0: 2,5-dimethylfuran; P: C7H10 + coelution without attribution; Q: co-elution of pyridine + without attribution; R: toluene; S: possibly co-elution of ten years + without attribution; T: 2-ethyl-5-methylfuran; U: a methyl pyridine; V: a methyl pyrrole; W: a xylene; X: without assignment - with an alcohol functionality; Y: without assignment; Z: coelution of a xylene + without attribution; AA: without assignment; AB: a dimethyl pyrrole; AC: a dimethyl pyridine; AD: a dimethyl pyridine; AE: without attribution; AF: without assignment; AG: co-elution of ethyl methyl pyrrole + without attribution; AI: a distinct mass spectrum with no attribution (containing N), related to pyrrole; AJ: an unassigned but distinct mass spectrum (containing N), possibly an acetamide; AK: an unassigned but distinct mass spectrum (containing N), related to pyrrole; AL: an unassigned but distinct mass spectrum (containing N), related to pyrrole; AM: an unassigned but distinct mass spectrum (containing N), related to pyrrole. The observed mass spectra of peaks AI to AM are not seen in the prior art binder data that did not have a polyamine component.
Procedure for the evaluation of tensile strength in the dry state and in those exposed to weathering. When assessing its tensile strength in the dry and "exposed" state, the curdling compositions containing glass beads prepared with a given binder provide an indication of the probable tensile strength and probable durability, respectively, of a fiber product. glass prepared with that specific binder. The expected durability is based on the tensile strength ratio in the state of the shell exposed to weathering: tensile strength in the dry state. The cups are prepared, exposed to weathering and tested as follows, for a mixture of hexamethylenediamine-dextrose binder, for example.
A shell (Dietert Foundry Testing Equipment; Heated Shell Curing Accessory, Model 366, and Shell Mold Accessory) is set to a desired temperature, usually 425 ° F, and allowed to warm for at least an hour. Although the shell is heating up, approximately 100 g of an aqueous binder (usually with 15% solids in the binder) is prepared (as described in Example 7, for example). Using a large glass, 727.5 g of glass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140, 106-212 microns - # 7 from Potters Industries, Inc.) are weighed by difference. The glass spheres are poured into a clean and dry mixing vessel, the vessel being mounted on an electric mixer holder. Approximately 75 g of aqueous binder is slowly poured into the glass microspheres in the mixing vessel. The electric mixer is switched on and the glass / binder mixture is stirred for one minute. Using a large spatula, the sides of the agitator (mixer) are scraped to remove any agglomerate of binder, while scraping the edges where the glass microspheres are at the bottom of the container. The mixer is then switched on again for another minute and the stirrer (mixer) is then removed from the unit, after which the mixing vessel containing the glass / binder mixture is removed. Using a large spatula, remove as much of the binder and glass beads that adhere to the agitator (mixer) as possible and stir the glass / binder mixture in the mixing vessel. The sides of the container are then shaved to mix any excess binder that may have accumulated on the sides. At this point, the mixture of glass microspheres / hexamethylenediamine-dextrose binder is ready to be molded into a mold.
The slide slides are checked to be aligned within the bottom mold plate. Using a large spatula, a mixture of glass microspheres / hexamethylenediamine-dextrose binder is then quickly added to three mold cavities within the mold. The mixture surface in each cavity is leveled, while scraping away the excess mixture to have a uniform surface area of the mold. Any inconsistencies or flaws that exist in any of the wells are filled with an additional mixture of glass microspheres / hexamethylenediamine-dextrose binder and then leveled. When a mixture of glass microspheres / hexamethylenediamine-dextrose binder is placed in the cup cavities, and the mixture is exposed to heat, curing begins.
As the handling time can affect the test results, just as molds with two different curing layers can be produced, for example; the cups are prepared consistently and quickly. With the shell filled, the upper plate is quickly placed on the lower plate. Simultaneously, or quickly thereafter, the curing time is measured using a stopwatch, during which time the temperature of the lower plate varied between approximately 400 ° F (204.4444444 ° C) to approximately 430 ° F (221 , 1111111 ° C) while the upper plate temperature varied between approximately 440 ° F (226.6666667 ° C) and approximately 470 ° F (243.3333333 ° C). After seven minutes have elapsed, the upper plate is removed and the slides are pulled out so that all three cups can be removed. The freshly prepared casks are then placed on a wire mesh, adjacent to the casing plate, and allowed to cool to room temperature. Then each mold is labeled and individually placed in a suitably labeled plastic storage bag. If the molds cannot be tested on the day they were prepared, the plastic bags containing the molds are placed in a desiccant unit.
Conditioning Procedure (Exposure to Weathering) for Chillings: A Blue M humidity chamber is turned on, then adjusted to provide weathering conditions of 90 ° F (32.22222222 ° C) and a relative humidity of 90% (ie, 90 ° F (32.22222222 ° C) / 90% rH). The water tank on the side of the humidity chamber is checked and filled regularly, usually whenever it is turned on. The humidity chamber is allowed to reach the specified weathering conditions for a period of time of at least 4 hours, with a day's equilibrium period being typical. The shells to be exposed to weathering are quickly loaded (since while the doors are open, both humidity and temperature go down), one at a time through the open doors of the humidity chamber to an upper shelf, equipped with slits, the humidity chamber. The moment when the cups were placed in the humidity chamber is recorded, and the weathering is conducted over a period of 24 hours. Then the humidity chamber doors are opened and one set of cups is quickly removed and placed individually in respective plastic storage bags, which are completely sealed. Generally, one to four sets of cups at a time are exposed to weathering, as described above. The shells exposed to weathering are immediately taken to the Instron chamber and tested.
Test Procedure for Breaking the Dies: In the Instron chamber, the dough test method is loaded on the Instron 5500R machine, while ensuring that the appropriate load cell is installed (ie Static Load Cell). 5 kN) and the machine is allowed to warm up for fifteen minutes. During this time, the test cup fasteners are checked to see if they are installed on the machine. The load cell is zeroed and balanced, and then a set of molds is tested each time as follows: A mold is removed from its plastic storage bag and is then weighed. The weight (in grams) is then entered on the computer associated with the Instron machine. The measured thickness of the die (in inches) is then entered, as the sample thickness, three times into the computer associated with the Instron machine. A sample of mold is then placed on the fasteners on the Instron machine, and tests are initiated using the keyboard on the Instron machine. After removing the sample from the mold, the measured breaking point is entered into the computer associated with the Instron machine, and testing continues until all of the molds in the set have been tested.
Effect of the Carbohydrate: Polyamine Reagent Ratio on the Properties of the Mold. The cups were made with varying ratios of dextrose monohydrate (DMH) to hexamethylenediamine (HMDA) with a silane additive (ISI0200) and were examined as described above, with a test speed of 25 mm / minute. The weight ratios tested include 90/10, 85/15, 80/20 and 75/25, respectively.

Example: Tests with Glass Wool (Fiberglass) Comparison of the qualities of two glucose-hexamethylenediamine binders with a standard binder in terms of cure and stiffness on a glass wool product 5 ((Ac + 032 100 mm 1200 mm) width; 32 kg / m3 - 15 m / minute) were conducted by measuring the resistance to separation and density Binder 1: 85% glucose - 15% hexamethylene diamine 10 Binder 2: 90% glucose - 10% hexamethylene diamine The Resistance to Common Separation (Before being autoclaved) and Resistance to Separation after Exposed to Weathering (After autoclaved) can be measured as described in international patent application Publication No. WO 2008/089851 or WO 20009019235.



glucose-hexamethylenediamine. Conclusions: With the two glucose-hexamethylenediamine binders, the results of resistance to separation (which is a resistance to longitudinal traction) showed a significant improvement; and a significant improvement was observed in three other stiffness tests ("60o" test - buckling measured when supported at 60 ° against a rail; "table" test - buckling measured against a horizontal plane; and Acermi test - measured buckling 35 cm from the edge of a table ". Example: Particle Board Test Comparisons of the qualities of the particle board produced using a urea-formic aldehyde binder (UF E0) and using a carbohydrate-polyamine binder (hexamethylene diamine) were conducted under the following conditions: Board size: 350 x 333 mm and mainly 10 mm thick (2 x 20 mm) Plate temperature: mainly 195 ° C, but also 175 and ~ 215 ° C. Pressure: 3.5 MPa (35 bar) Nominal - Actual 35 kg / cm2, 56 bar (5600 kPa) to be achieved Target density: 650 kg / m3 Preform prepared before pressing.

All the prepared boards appeared to be of high quality; no cracking or shedding of gases was observed. The boards produced with this carbohydrate-polyamine formulation match the urea-aldehyde 5 formic board when they are cured for 150 seconds

权利要求:
Claims (34)
[0001]
1. Method of preparing a composite wood board comprising a collection of material comprising cellulosic fibers bonded with a polymeric, heat-cured, cured binder, characterized by comprising: (i) preparing an aqueous binder solution containing reagents to produce the polymeric, heat-bonded binder , cured, wherein the reagents include a reducing sugar and a nucleophile R1-Q-R2, wherein: Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of which is optionally substituted; Ri is selected from the group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl and an alkoxide, and R2 is selected from the group consisting of an amine, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a sulfone, a sulfo, a sulfinyl and a sulfhydryl, provided that , when the nucleophile consists of polyethylene imine, the molar ratio of reducing sugar to the nucleophile is in the range of 1: 1 to 30: 1; (ii) disposing the aqueous binder solution over a collection of material; (iii) drying the aqueous binder solution to form an uncured product; and (iv) thermally curing the uncured product comprising 3% to 25% dry binder solids (total uncured solids by weight) to form the composite wood board bonded with the cured, polymeric, thermal binder.
[0002]
2. Method, according to claim 1, characterized by the fact that preparing an aqueous binder solution includes at least one of the steps selected from the group consisting of: a) adding an amount of reducing sugar and an amount of the nucleophile such that weight ratio of the reducing sugar to the nucleophile is in the range of about 2: 1 to about 10: 1; b) adding the reducing sugar and the nucleophile to an aqueous solution; and c) adjust the pH of the solution to be within the range of about 8 to about 12.
[0003]
3. Method, according to claim 1, characterized by the fact that the cured polymeric, thermoset binder is free formaldehyde.
[0004]
4. Method according to claim 1, characterized by the fact that neither formaldehyde nor phenol is used as a reagent.
[0005]
5. Method, according to claim 1, characterized by the fact that cellulosic fibers comprise material selected from the group consisting of wood chips, sawdust, wood pulp, crushed wood, jute, linen, hemp and straw.
[0006]
6. Method according to claim 1, characterized by the fact that the weight ratio of the reducing sugar to the nucleophile is in the range of about 2: 1 to 10: 1.
[0007]
7. Method, according to claim 1, characterized by the fact that the reducing sugar is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone and their mixtures.
[0008]
8. Method according to claim 1, characterized in that Ri and Rs form covalent bonds with the reducing sugar to form the polymeric binder.
[0009]
9. Method according to claim 1, characterized by the fact that: Ri is selected from the group consisting of an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl and an alkoxide, and Rs is selected from the group consisting of an amine, an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphono, a hydroxyl, a sulfone, a sulfo, a sulfinyl and a sulfhydryl.
[0010]
10. Method according to claim 1, characterized by the fact that: Ri is selected from the group consisting of an amine, an azide, a cyanate, an isocyanate, a thiol, a disulfide, a thiocyanate, a halogen, a haloformyl, a carboxyl, a carboxylate, a hydroxyl and an alkoxide, and Rs is selected from the group consisting of an amide, an imine, an imide, a nitro, a nitrate, a pyridine, a phosphate, a phosphone, a hydroxyl, a sulfone, a sulfo, a sulfinyl and a sulfhydryl.
[0011]
11. Method according to claim 1 characterized by the fact that: Ri is selected from the group consisting of an azide, a thiol, a halogen, a carboxyl, a carboxylate, a hydroxyl and an alkoxide, and R2 is selected from the group that it consists of an imine, a pyridine, a phosphate, a phosphono, a hydroxyl, a sulfinyl and a sulfhydryl.
[0012]
12. Method according to claim 1, characterized by the fact that R1-Q-R2 does not consist of polyethylene imine.
[0013]
13. Method according to claim 1, characterized by the fact that neither RI nor R2 is an amine.
[0014]
14. Method according to claim 1, characterized in that R1-Q-R2 is a primary amine having only one primary amine group.
[0015]
15. Method according to claim 1, characterized by the fact that Q is an alkyl selected from the group consisting of C2-C24.
[0016]
16. Method according to claim 1, characterized by the fact that Q is an alkyl selected from the group consisting of C2-C8.
[0017]
17. Method according to claim 1, characterized by the fact that Q is an alkyl selected from the group consisting of C3-C7.
[0018]
18. Method according to claim 1, characterized by the fact that Q is a Ce alkyl.
[0019]
19. Method, according to claim 1, characterized by the fact that Q is a cycloalkyl selected from the group consisting of cyclohexyl, cyclopentyl and cyclobutyl.
[0020]
20. Method according to claim 1, characterized by the fact that R1-Q-R2 is 2 - [(2-aminoethyl) amino] ethanol.
[0021]
21. Method according to claim 1, characterized by the fact that each of Ri and R2 is thiol.
[0022]
22. Method according to claim 1, characterized in that Ri is an amine and R2 is an amine, an amide, an imine, or an imide.
[0023]
23. Method according to claim 1, characterized by the fact that Ri is an amine and R2 is an amine.
[0024]
24. Method, according to claim 1, characterized by the fact that the molar ratio of the reducing sugar to the nucleophile is in the range of 1: 1 to 30: 1.
[0025]
25. Method, according to claim 1, characterized by the fact that the molar ratio of the reducing sugar to the nucleophile is in the range of 2: 1 to 10: 1.
[0026]
26. Method, according to claim 1, characterized by the fact that the molar ratio of the reducing sugar to the nucleophile is in the range of 3: 1 to 6: 1.
[0027]
27. Method according to claim 1, characterized by the fact that the preparation of the aqueous binder solution includes adjusting the pH of the aqueous binder solution to be within the range of 8 to 12.
[0028]
28. Method according to claim 1, characterized by the fact that the aqueous binder solution has an alkaline pH.
[0029]
29. Method according to claim 1, characterized by the fact that the cured polymeric, thermoset binder is insoluble in water.
[0030]
30. Method, according to claim 1, characterized by the fact that the cured polymeric, thermoset binder absorbs light intensely at 420 nm.
[0031]
31. Method according to claim 1, characterized by the fact that the aqueous binder solution is acid-free.
[0032]
32. Method, according to claim 1, characterized by the fact that the cured material collection and the polymeric, thermoset binder further comprise a material selected from the group consisting of a compound containing silicon, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane , aminoethylaminopropyltrimethoxysilane, an aminofunctional oligomeric siloxane and mixtures thereof.
[0033]
33. Method according to claim 1, characterized by the fact that the cured material collection and polymeric, thermosetting binder further comprise a corrosion inhibitor selected from the group consisting of anti-dust oil, monoammonium phosphate, metasilicate sodium pentahydrate, melamine, tin (II) oxalate, and liquid methylated hydrogenated silicone emulsion.
[0034]
34. Method according to claim 1, characterized by the fact that the binder further comprises a non-aqueous humidifier

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-03-17| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-09-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US33245210P| true| 2010-05-07|2010-05-07|

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US61/332,452|2010-05-07|

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PCT/EP2011/057364|WO2011138459A1|2010-05-07|2011-05-07|Carbohydrate binders and materials made therewith|

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